New azodyestuffs and process of making same



Ill

Patented Sept. 22, 1931 UNITED STATES PATENT] OFFICE GEORG KALISGHER, OF FRANKEORT-ON-THE-MAIN, AND

CARL SGHULTIS, or FRANK- FORT-ON-THE-MAIN-FEGHENHEIM, GERMANY, ASSIGNORS 'TO GENERAL ANILINE WORKS INC., NEW YORK, N. Y., A CORPORATION OF DELAWARE I NEW AZQDYESTUFIS AND PROGESSOF MAKING SAME No Drawing. Application filed June 8, 1929, Serial No. 369,520, and in Ger1nany June 16, 1 928.

The present invention relates to new azodyestufls and to a process of preparing the same. More particularly it relates to azodyestufis corresponding to" the general formula X-OdIiQ-bhN-R I dyestufis thus obtained correspond to the,

general formula:

x-onn-Qnmen wherein X means hydrogen or an alkyl group, n the number 8 or 10,'Y hydrogen, halogen, an alkyl or an alko-xy group and R an aromatic residue capable of combining with diazo compounds and containing at least one sulfonic group.

These dyestufls dye wool from an acid bath 1 yellow to red to violet tobrownish' shades. They are distinguished by the purity and brightness of their shades and by a remarkably good fastness to washing and milling. The dyestufis containing a cyclohexyl-ring in their molecule corresponding, for instance, to the general formula:

y H! I H: 1

Ha Y

H2 wherein Y and B have the aforesaid signification, dye generally more yellowish shades than those containinga cyclohexenyl nucleus, the other properties of both groups of dyestuffs being very similar.

In order to further illustrate our invention the following examples are given the parts being by weightand all'temperatures in centigrade degrees. Butwe wish it to be understood that we are not limited to the particular conditions or specific products mentioned therein.

Example 1.

17.8 parts of 4-a1nin0-2.3.4.5-tetrahydrod1phenyl are dissolved in about 80 parts of hot Water by the addition of hydrochloric acid and the solution is introduced into a nnxture of 23 parts of hydrochloric acid (specific gravity 1.155) and ice. The suspension thus formed is diazotized atabout 510 with a solutlon of 6.9 parts of sodium nitrite in about parts of water. The diazo solution obtained thereby is combined at'about 10 with a solution of 24.6 parts of the sodium salt of 2-hydroxynaphthalene-7-sulfonic acid and 30 parts of sodium carbonate.

The dyestuff thus produced corresponds probably to the formula:

It'dyes wool from an acid bath clear red shades.

v E sample 2 20.5 arts of 4-amino-3-methoXy-1.2'.3 .4.5 .6- exahydro-diphenyl are dissolved by boiling in 12 parts of hydrochloric acid (specific gravity=1.155) and 250 parts of water. The hot solution is poured onto ice. The pulp of crystals is mixed with 23 parts of hydrochloric acid (specific gravity 1.155) and diazotized at- 10 with a solution of 6.9 parts of sodium nitrite in parts of Water, whereby the mixture is dissolved. The diazo solution thus obtained is combined at 10 to 15 with a solution of 24 parts of the sodium salt of lnaphthol-4-sulfonic acid and 32 parts of sodium carbonate.

In this manner a dyestu'fi' is produced which yields on wool fast bright red shades and corresponds prob'ably to the formula:

Example 3 solution of 6.9 parts of sodium nitrite in 50 parts of water. The diazo so-lutionisallowed The formed dyestufi' corresponds probably to the formula:

It dyes wool clear yellow shades.

Example 1;

A hot solution of 18.9 parts of l-ainino-Elmethyl-hexahydro-diphenyl in 35 parts of hydrochloric acid (specific gravity=1.155) and 300 partsof water is poured onto ice. The suspension of the hydrochloric salt of the base is diazotized at about 10 with a to' run at 10 into a solution, of.44.5 parts of the sodium salt of 1-benzoylamino-8na phthol-4.6-disulfonic' acid and 43 parts of sodium carbonate in 500 parts of water. The dyestufl' is isolated by the addition of 25 parts of common salt. It corresponds to the formula on i s-o o{ SOaH It dyes wool bright red shades of a good .fastness to washing, milling and light.

In the following-table there are cited some further components suitable; for the combination according to our process and the properties of thedyestuffs obtained therefrom.

Diaz o compound of Combined with Color of the .dry and pulverized dyestuff Color of solu- Color of solution in dilute tion in sulcaustic alkali v i'uric acid solution solution Qolor of solu- Dyeing in tion in water wool 1-naphthol-4-sulfonic acid 1-naphthol-7-su1fonic acid 2-naphthol-3.fi-disnlfonic acid l-naphtkiol-El.fi-disulfonic acid 2.S-dihydroxy-naphthalene-6 sulfonic acid 2-amin0-8-naphthol-(i-sulfonic acid (acetic acid) l-toluene-sulfamino 8- n a p h thol-3.6-disulfonic acid 1-benzene-snlfarnino 8- n a p h thol-ifi-disulfonioaeid 1(25-dichloro-benzoy1 amino) 8-naphtliol-4.6-disulfonic'acid 2-phenyl-amino-S-nziphthoL6- sulfonic acid 1-amino-2-(4'nitrophenyD-azo- S-naphthoLSfidisulfonic acid p-(cyclohexylaniline) Do Do Dark red Reddish brown Reddish brown Reddish brown Yellowish red Red Dark brown Yellowish red Brownish red Bluish red Violet black Bluish xcd Yellowish red Yellowish red Yellowish red Violet Claretred Bluisli red Bluish red Claret red Bluish red Bluishgreen Ycllowish red Orange YOllOWlSll 1 ed Scarlet Red Rcddish brown Red Red

Bright red Orange Orange Yellowish red Yellowish red Rcd Ycllowish red Red Yellowish red Orange Orange Yellowisli led Orange Red Yellowish red Red Red

Yellowish red Red dis h brown Blue Orange Reddish brown Rcddish blue Brown Grccnisll blue 1 l '4 m5. ,6 a :1

dColor (A! the C 1 f 1 f 1(giolor 0:1 ilolitl- Color of solue ry an pu ;o are so uon in u e tion in sul- D ein in Dmo compound combmed Wlth verized dyetion in water caustic alkali (uric acid woo l stuff solution solution 4-amino-4'methyl-tetral-naphthol-Wsulfonic acid Reddish Yellowisli red 'Yello'w'ish red Violet Yellowi h r d hydrodipheuyl 5 v brown g 4-airpiirlio-te t ra h y d ro- 2-naphthol-3 6-disuliomc acid R gidl b Red yellowish red Claret red Bluish red ip eny v rown I Do 2.8-dihydroxy naphthalene-fi- Rcddish Red Red Reddish blue Bluish red 1 tsullionic' aiilfd 8 h brown Do 0 119119 SH o- P Violet black Bluish red Bluish red V l t (tzl o lifiigisulionic aclid r I et Claret Do 5 i0 0T0 enzoy amino Dark claret Bluish red Yellowish red 1 8-ugphtl1ol-4.6-clisulfo n ic red I C amt red Bhnsh red 80! Y t V DO D YD- B ac Greenish blue 'Greenish blue 8-naphthol-3.6-disulion ic acid ,Brown reemsh. blue 4-amiuo-3mcthyl-heKal-naphtholi-sulfonic acid Yellowish red Yellowish red Orange Bluish red Yellowi'sh red hydrodiphcnyl i Do 2-nao th0 -3.6-d su n a d Red Red Yellowish red Red yellowish red D0 1.8-d yd o y n ph a w- Black Yellowish red Yellowish red Violet Reddish sulionic acid v 7 r c I violet Do -am on p -sulfomc Violet black Red Red Claret red Red acid (in sodium carbonate r V i solution) h D0 l-arn no-8 gaphthol-2A- s Dark brown Bluish red Red 'Bluish red Reddish ouic aei v viokt D0 1 0 D Y Ycllow Yellow Yellow Yellow Greenish v methyl-5-pyrazplone i r venow D0 l-toluene sulfamluo-B-P aph- Reddish Bluish red Bluish red Bluish red Bluish red V tl1ol-3.6-disi 1lfonlc acid b w 7 i V LirDo l -benz0y1aml n0-8 -I 1D t Dark claret Bluisli red Bluish red 4 Blue d ,1 $.{i-dl5l1lf0fil0 said I Bred a Do 0 e e 511 09 V fi ed r Red Red Clarctrcd 8-ugpl1thol-3fi-di sulfonic Blmsh red am e l I Do 1-(2'5dichl0r0 enzby miml Bluish red Red Yellowish red Violet 1 d S-ugphthol-iG-d i sul I o n ie Bhmh m y aci v Do fl-ph nyl-a -B- Dht Dark brown Brownish redo Brownish red Claret red Brown su onie aci D 2-(4'tolyl-an1in0) -8-naphth0 Dark brown Brownish red Brownish red Bluish red Brown 6-sullonic acid r 4 a min 0 3 rm 6 t 11 y 1 2-naphth0l-7-sull0nic acid Reddisb Red Red Violet Red tetrahydrodiphenyl brown n r l i V 1-naDhth0l-3.G dlSlllfOlllC acid Dirk reddish Bluish red Yellowish red Cl ret red Blui h red rown D0 3d Y flD Brown Red Red Blue Claret red sulionic acid D0 2-ammo-8-naphth0l-fi-sulio lc Blackish Yellowish red Yellowish red Dull claret R d acid (acetic acid) brown 1 i 7 red a Do l-toluene sulfamino-8-uaphth0l- Violet black Bluish red 'Bluish red Violet Rcddish' 4.6-disulfonic acid 1 violet D0 v l-(25'- lichloro benzoyl amm0 Black Claret red Claret red Blue Violet S-ugphthol-iii-dxsulion1c -ac1 Do 1-(2'-chloro-5-su lio phenyD- Orange Reddlsh Yellow Orange Reddish B-methyl-li-pyrazclone yellow yellow 4. i o-3-methoxy- 1-naphthol-4-sulf0n1c acid Yellowish red Bluish red Yellowish red Bluish red Bright red hexahydrodiphenyl I r 1 o r2-I1aphth01}3.fi-dlSllll'OlllQ acid Regldish Bluish red Yellgwish Bluish red Bluish red lOtVll re Do l-amino-8-naphtllo1-3.6-disul- Dark brown Bluish red 'Red Bluish red Reddish ionic acid violet D0 2-aI]2liI108-Dfiphth01-G-SUHODK! Dark brown Red Yellowisll red Claret red Brownish red 7 ac t Do 2.8-dihydroxy-napl1thalene-fi- Brownish Bluishred Red Blue Bluish red sulfonic acid black r r r Do 1 ;l lor0-8- I(11aphtliol-3.G-disul- Bluishred Bluish red Yellowish red Violet Bluish icd I onic aoi D l-toluene'sull'amin0;8-naphth0l- Claret red Bluish red Red 7 'Violet Reddish 3.6-disulionic acid I I "inlet I Do l-b enzoyl-ammo-S-naphthol- Bluish red Bluish red Yellowish red Claret red Bluish red 3,6-disullonic acid Do 1-(25di hl r0 nzoij amm Reddish Bluish red Yellowish red Claret red Reddish S-FafiphllhOl-i.fi-dlslllfolllc brown violet 301 D l-benzene sulfamino-Smaphthol- Reddish Red Red Violet Reddish 4.6-disulfouio acid brown violet 4 -amirio-3-methoxyl-naphthol-7-sulfon1c acid Brown Bluish red Ycllowish red Violet Bluisli red tetrahydrodipliouyl I I r a D 2-naphtl1ol-3.fi-dlsulionic acid Dull violet Bluish red Yellowlsh red Violet Claret red D 2.8-dihydroxy naphthalene-(i- Black Claret Red, Blue Violet sulfonic acid i Do l-amino-S-naphthol-3.6-disul- Brownish Reddish Claret red Reddish blue Violet ionic acid black violet 1 v D o 2-phenyl-amino-8-naphthol-6- Black Claret red Red Blue Reddish sulionic acid l l l brown Do" l-(4-sulfophcnyl)-3-methyl-5- Yellowish red Orange Yellow Yellowish rcd Reddisli pyrazolone 1 7 yellow i Do l-toluene suliamlno-S-naphthol- Violet Violet Claret red Blue 'Bluish violet 3.6;disulfonic acid Do u 1-(25dichloro benzoyl-amino) Dark violet Claret red Yellowish red Blue Violet 8-ugphthol-4.6-disulfonio I aei r 4-amino-3 ehloro-tetra- 1-uaphthol-4-sulionic acid Black Bluish red Claret red Blackish blue Red hydrodiphenyl a r L i "Do L8-dihydroxy naphthalene-L Blackish Red Bluishred Violet Violet suliouic acid violet I Do 2-amiuo-8-naphthol fi-sulionic Reddish Red Yellowlsh red Claret red Rcddish o acid brown brown iii ' We claimi 1. A process which comprlses diazotlzing anaromatlcannneof the generalformula wherein X means hydrogen or an alkyl group, n the number 8 or 10 andY hydrogen, halogen, an alkyl or an alkoxy group, and combining the diazo compound thus: obtained with a combining component of the naphthalene and pyrazolone series containing at least one sulfonic group. V

2. A process which comprises diazotizing a' 4-cyclo-hexyl-1-amino-benzene compound of the general formula:

wherein Y means hydrogen, halogen, an alkyl or an alkoxy group, and combining the diazo compound thus obtained with a combining component of the naphthalene and pyrazolone series containing at least one 'sulfonicgroup.

3. A process which comprises diazotizing a 4-cyclo-hexy1-1-amino-benzene compound i of the general formula:

wherein Y means hydrogen, halogen, an alkyl or an alkoxy group, and combining the diazo compound thus obtained with a nap'hthol sulfoni-cacid of the general formula:

Naphthalene 2 wherein Zmeanshy-drogen, a hydroxy, amino, arylmino or acyl-arninogroup and m means the number 1 or 2.

LA process which comprises diazotizing 4-cyclo-heXyl-2-methyl-1amino-benzene of the formula:

H1 c H2 7 I I i OYO 11 1 El: I v v I i and combining thediazoicompound thus obtained 'with' 1-benzoyl-amino-8-naphthol-4.6- disulfonic acid of the formula:

' HOaS sogn 5. A'snew compoundsthe azo dyestuffs of the general formula:

XCaHn-QN=NR, w m

wherein X meanshydrogen or an alkyl group,

n the number 8101' 10, Y hydrogen, halogen, an alkyl or an alkoxy' group and R a residue of the naphthalene and pyrazolone series capable of combining with diazo compounds and containing at least one sulfonic group, which compounds are when dry colored powders, soluble in water, dyeing wool from an acid bath yellow, redto violet and brown shades-of an excellent fastn ess to washing and milling.

6. As new compounds the azo dyestufis of the'general formula:

wherein Y means hydrogen, halogen, an alkyl or an alkoxy'group, Z hydrogen, a hydroxy amino, arylamino "or iacylamin'o groupa-nd m the nu'mber l or 2, which compounds are when idry colored powders, soluble in water, dyeing wool from an acid bath orange, red to violet and brown shades of an excellent fastness to washing and milling. 8. As a new compound the azo dyestuif of the formula:

which compound is when dry a red powder, 7 soluble in water to a red solution, dyeing wool from an acid bath bright red shades of a good fastness to washing, milling and light.

In testimony whereof, we afiix our signatures.

GEORG KALISGHER. CARL SOHULTIS.

H: H: on NH-C o-O H z N=N i H 1 I H, Ha E018 g Certificate of Correction Patent No. 1,823,943. I Granted September 22, 1931, to (I GEORG KALISCHER ET AL.

It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 4:, claim 7, for the last equation of the formula (SO H) read (80 E and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 15th day of December, A. D. 1931.

[SEAL] M. J. MOORE,

Acting Gammissioner of Patents.

Certificate of Correction Patent No. 1,823,943. Y Granted September 22, 1931, to

GEORG KALISCHER ET AL.

It is hereby certified that Certificate of Correction issued December 15, 1931, was erroneously drawn as to the last equation of the formula on page 4, claim 7 and that this last equation of the formula should read (sO H) m and that the said certificate should be read With this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 26th day of January, A. D. 1932.

[SEAL] M. J. MOORE,

Acting Commissioner of Patents. 

